Acid disazo dyestuffs containing a substituted thiophene middle component

ABSTRACT

Dyestuffs which in the free acid form correspond to the formula ##STR1## wherein A represents the radical of an aromatic carbocyclic or aromatic heterocyclic diazo component, 
     B represents the radical of a carbocyclic or heterocyclic coupling component, 
     X represents OH, --NHSO 2  --R 3 , --N(R 4 )--alkylene-SO 3  H, --N(R 4 )-arylene-SO 3  H, --N(R 4 )-arylene--CH 2  --SO 3  H or --N(R 4 )-arylene-SO 2  --NH-SO 2  -R 3  and N(R 4 )-alkylene-O-SO 3  H, 
     R 1  represents alkyl, aryl, carbalkoxy or hydrogen, 
     R 2  represents carbalkoxy, carboxylic acid amide or cyano, 
     R 3  represents alkyl or aryl, 
     R 4  represents hydrogen or alkyl, 
     m and n represent 0, 1 or 2, 
     p represents 0 or 1 and 
     m+n represent 1 or 2 
     are suitable for the dyeing of natural and synthetic fibre materials, particularly for the dyeing of polyamide fibre materials.

The invention relates to disazo dyestuffs which in the form of the free acid correspond to the formula ##STR2## wherein A represents the radical of an aromatic carbocyclic or aromatic heterocyclic diazo component,

B represents the radical of a carbocyclic or heterocyclic coupling component,

X represents OH, --NHSO₂ --R₃, --N(R₄)--alkylene--SO₃ H, --N(R₄)--arlyene--SO₃ H, --N(R₄)--arylene--CH₂ --SO₃ H or --N(R₄)--arylene--SO₂ --NH--SO₂ --R₃ and N(R₄)--alkylene--O--SO₃ H,

R₁ represents alkyl, aryl, carbalkoxy or hydrogen,

R₂ represents carbalkoxy, carboxylic acid amide or cyano,

R₃ represents alkyl or aryl,

R₄ represents hydrogen or alkyl,

m and n represent 0, 1 or 2,

p represents 0 or 1 and

m+n represent 1 or 2.

Suitable radicals A of a heterocyclic diazo component are those of the thiazole, benzthiazole, thiadiazole, triazole, pyrazole or thiophene series, which can optionally be substituted by C₁ -C₄ -alkyl, aryl, halogen, cyano, optionally substituted carbamoyl, carbalkoxy or nitro.

Suitable radicals A of aromatic-carbocyclic diazo components are those of the benzene or naphthalene series which can be substituted by halogen, cyano, carbalkoxy, trifluoromethyl, alkyl, alkoxy, hydroxyl, thiocyanato, alkylsulphonyl, arylsulphonyl or aralkylsulphonyl, carbamoyl or sulphamoyl radicals.

Suitable radicals B of a carbocyclic or heterocyclic coupling component are ##STR3## wherein R₅ represents alkyl, aralkyl or hydrogen,

R₆ represents alkyl, aralkyl or hydrogen,

R₇ represents hydrogen, alkyl, alkoxy, halogen, alkylsulphonyl, aralkylsulphonyl, arylsulphonyl, sulphamoyl, a sulphonic acid radical, carbamoyl, carbalkoxy or acylamino,

R₈ represents hydrogen, alkyl, halogen, alkoxy or acylamino,

R₉ represents hydrogen, alkyl, alkoxy, halogen, cyano or the sulphonic acid radical,

R₁₀ represents alkyl, phenyl or hydrogen,

R₁₁ represents hydrogen or alkyl,

R₁₂ represents cyano, hydrogen, alkyl, phenyl, carbalkoxy or carboxylic acid amide,

R₁₃ represents hydrogen, alkyl or aryl,

R₁₄ represents hydrogen or alkyl,

R₁₅ represents hydrogen, alkyl, hydroxyl, phenyl or carbalkoxy and

R₁₆ represents cyano, carboxylic acid amide or carbonalkoxy.

The carbamoyl radicals R₂, R₇, R₁₂ and R₁₆ or the sulphamoyl radicals R₇, as well as the carbamoyl radicals and sulphamoyl radicals which may represent substituents of A, are optionally monosubstituted or disubstituted by alkyl, aralkyl, aryl or cycloalkyl or the radical of a heterocyclic ring, and the substituents, together with the nitrogen of the carbamoyl or sulphamoyl radical and optionally a further hetero-atom can be cyclised to form a five-membered or six-membered heterocyclic ring. Radicals of such heterocyclic rings are, for example ##STR4##

Suitable alkyl groups R₁, R₃, R₉, R₁₀, R₁₂ and R₁₅ are, for example, unsubstituted C₁ -C₄ -alkyl radicals, for example methyl, ethyl, propyl and iso-butyl.

Suitable alkyl radicals as substituents of A, R₄, R₇, R₈, R₁₁, R₁₃ and R₁₄, or of the alkylsulphonyl groups, the alkylsulphonylamino groups, the carbamoyl radicals, the sulphamoyl radicals or the carboxylic acid esters are, for example, those with 1-4 C atoms, which can optionally be substituted by halogen, cyano, hydroxyl or C₁ -C₄ -alkoxy, for example methyl, ethyl, propyl, isobutyl, hydroxyethyl, cyanoethyl, chloroethyl, 2-hydroxylbutyl, methoxyethyl, propoxymethyl or butoxymethyl.

Suitable alkyl groups R₅ and R₆ are, for example, those with 1-4 carbon atoms, which can optionally be substituted by halogen, cyano, hydroxyl, C₁ -C₄ -alkoxy, benzyloxy, phenoxy, C₁ -C₄ -alkylcarbonyloxy, C₁ -C₄ -alkoxycarbonyloxy, phenoxycarbonyloxy or arylcarbonyloxy, such as, for example, benzoyloxy, or by the sulphonic acid radical, for example methyl, ethyl, propyl, methoxymethyl, ethoxyethyl, hydroxyethyl, cyanoethyl, chloroethyl, phenoxyethyl, benzyloxyethyl, acetoxyethyl, propionyloxyethyl, ethoxycarbonyloxyethyl, butoxycarbonyloxyethyl, benzoyloxyethyl, phenoxycarbonyloxy ethyl or the --CH₂ --CH₂ --SO₃ H radical.

Suitable aryl radicals R₁, R₃, R₆, R₁₀, R₁₂ and R₁₅ of the carbamoyl groups and sulphamoyl groups and of the arylsulphonyl groups are, in particular, phenyl or naphthyl radicals which are optionally substituted further by phenyl, C₁ -C₄ -alkyl, nitro, halogen or C₁ -C₄ -alkoxy, for example phenyl, 1-naphthyl, 2-naphthyl, p-biphenyl, 4-chlorophenyl, 2,4-dichlorophenyl, 4-ethoxyphenyl, o-, m- and p-tolyl, 4-nitrophenyl or 4-ethylphenyl.

Suitable aryl groups R₁₃ are in particular phenyl or naphthyl radicals which are optionally substituted further by phenyl, C₁ -C₄ -alkyl, nitro, halogen, C₁ -C₄ -alkoxy or the sulphonic acid radical, for example phenyl, 1-naphthyl, 2-naphthyl, p-biphenyl, 2-chlorophenyl, 4-chlorophenyl, 2,5-dichlorophenyl, 2-nitrophenyl, 3-nitrophenyl, o-, m- and p-tolyl, 4-ethoxyphenyl, 3-phenylsulphonic acid, 3-phenyl-4-chlorosulphonic acid and 4-phenyl-3,4-dichlorosulphonic acid.

Suitable aralkyl groups as substituents of the sulphamoyl, carbamyl or aralkylsulphonyl groups are, in particular, benzyl or 2-phenylethyl groups. The phenyl radical of these groups can optionally be substituted further by C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, halogen or cyano, such as, for example, benzyl, 2-phenylethyl, p-ethylbenzyl, p-methoxybenzyl, 2,4-dichlorobenzyl, 4-cyanobenzyl and p-bromophenylethyl.

Suitable aralkyl groups R₆ are, in particular, benzyl or 2-phenylethyl groups. The phenyl radical of these groups can optionally be substituted by C₁ -C₄ -alkoxy, halogen, cyano or the sulphonic acid radical, such as, for example, benzyl, 2-phenylethyl, p-methylbenzyl, p-methoxybenzyl, 2,4-dichlorobenzyl, 4-cyanobenzyl or 3-sulphobenzyl.

Suitable carbalkoxy groups R₁, R₂, R₇, R₁₂ and R₁₆ and carbalkoxy groups as substituents of A are, in particular, carbo-C₁ -C₄ -alkoxy, such as carbethoxy, carbo-iso-propoxy and carbomethoxy.

Suitable halogen atoms are fluorine, chlorine and bromine, especially chlorine and bromine.

Suitable alkoxy radicals R₇, R₈ and R₉ or alkoxy radicals as substituents A are, in particular, C₁ -C₄ -alkoxy, which can optionally be substituted by OH, halogen or cyano, such as, for example, methoxy, ethoxy, butoxy, 2-hydroxyethoxy, 2-cyanoethoxy or 2-chloroethoxy.

Suitable alkylene radicals in ##STR5## and ##STR6## are, in particular, C₂ -C₄ -alkylene radicals, for example --CH₂ --CH₂ --, ##STR7## or --CH₂ --CH₂ --CH₂ --CH₂.

Suitable arylene radicals in ##STR8## are, in particular, 1,2-, 1,3- or 1,4-phenylene radicals.

The phenylene radicals can be substituted further, for example by alkyl, especially C₁ -C₄ -alkyl, by alkoxy, especially C₁ -C₄ -alkoxy, such as CH₃ -O- or C₂ H₅ -O-, or aralkoxy such as C₆ H₅ -CH₂ -O-, or by chlorine, bromine, cyano or nitro.

A suitable heterocyclic ring as substituent of a sulphamoyl or carbamoyl radical is, for example, the 2-sulpholane radical.

Suitable acyl radicals of the acylamino group R₇ and R₈ are, in particular, C₁ -C₄ -alkylcarbonyl, arylcarbonyl, C₁ -C₄ -alkylsulphonyl and arylsulphonyl. A suitable aryl radical is, in particular, the phenyl radical, which can optionally be substituted by C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, chlorine or cyano.

The following may be mentioned as examples of acyl radicals: acetyl, propionyl, methylsulphonyl, ethylsulphonyl, p-methylphenylsulphonyl, phenylsulphonyl, 2,5-dimethylphenylsulphonyl, 2-methyl-5-chlorophenylsulphonyl, p-ethoxybenzoyl, p-chlorobenzyl, o-chlorobenzyl or p-cyanobenzoyl.

A preferred group of these dyestuffs are those which in the form of the free acid correspond to the formula ##STR9## wherein B' represents the radicals ##STR10## R₁, R₂, R₅, R₁₀, R₁₁ and R₁₂ have the abovementioned meaning and

R₆ ' represents C₁ -C₄ -alkyl, CH₂ -CH₂ -SO₃ -H or 3-sulphobenzyl,

R₆ " represents hydrogen, C₁ -C₄ -alkyl, benzyl or 2-phenylethyl,

R₇ ' represents hydrogen, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, halogen or C₁ -C₄ -alkylsulphonyl,

R₁₇ and R₁₈ represent hydrogen, chlorine, bromine, cyano. C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, a carbamoyl or sulphamoyl radical, hydroxyl, trifluoromethyl or a C₁ -C₄ -alkyl-, a phenyl- or a benzylsulphonyl radical, R₁₉ represents hydrogen, C₁ -C₄ -alkyl, CF₃, Cl or Br and

R₂₀ and R₂₁ represent hydrogen, C₁ -C₄ -alkyl, Cl or Br.

A particularly preferred group of the dyestuffs of

the formula (II) are those which in the form of the free acid correspond to the formula ##STR11## wherein B" represents the radicals ##STR12## and R₆ ', R₆ ", R₇ ', R₁₁, R₁₉, R₂₀ and R₂₁ have the above-mentioned meaning,

R₁ ' represents methyl, ethyl, phenyl which is optionally substituted by Cl or NO₂, carbo-C₁ -C₄ -alkoxy or hydrogen,

R₂ ' represents carbon-C₁ -C₄ -alkoxy, cyano, CONH₂, CON(CH₃)₂ or CON(C₂ H₅)₂,

R₅ ' represents C₁ -C₄ -alkyl which is not substituted further, benzyl or hydrogen,

R₈ ' represents hydrogen, CH₃ --, C₂ H₅ --, --OCH₃, --OC₂ H₅, Cl or ##STR13## n=1, 2 or 3, R₁₀ ' represents methyl, ethyl or phenyl,

R₁₂ ' represents hydrogen, methyl, phenyl or carbomethoxy or carboethoxy and

R₁₇ ' and R₁₈ ' represent hydrogen, chlorine, bromine, cyano, C₁ -C₂ -alkyl, C₁ -C₂ -alkoxy, C₂ -C₄ -carboalkoxy, a carbamoyl or sulphamoyl radical which can be monosubstituted or disubstituted by C₁ -C₃ -alkyl, or a C₁ -C₄ -alkylsulphonyl, phenylsulphonyl or benzylsulphonyl radical.

Particularly preferred dyestuffs are, in particular, those of the formula ##STR14## wherein B"' represents the radicals ##STR15## R₅ ', R₆ ', R₆ ", R₈ ', R₁₀ ', R₁₂ ', R₁₇ ', R₁₈ ' and R₁₉ have the meaning mentioned and

R₁ " represents hydrogen, methyl of phenyl,

R₂ " represents carbomethoxy, carboethoxy, cyano or unsubstituted carbamoyl,

R₇ " represents methoxy, ethoxy, methylsulphonyl or hydrogen,

R₁₁ ' represents hydrogen or methyl and

R₂₀ ' and R₂₁ " represent hydrogen, methyl or chlorine.

Very particularly preferred dyestuffs are those which in the form of the free acid correspond to the formula ##STR16## wherein R₁ ", R₂ ", R₁₇ ', R₁₈ ' and R₁₉ have the abovementioned meaning,

V represents the groups ##STR17## and R₈ " denotes hydrogen, methyl, methoxy or acetylamino.

Further preferred dyestuffs are those which in the form of the free acid correspond to the formula ##STR18## or to the formula ##STR19## wherein B^(IV) represents ##STR20## X, R₁, R₂, R₅, R₈, R₁₀, R₁₁, R₁₂, R₁₄, R₁₅, R₁₆, R₁₇ and R₁₉ have the abovementioned meaning and

R₆ ''' represents hydrogen, C₁ -C₄ -alkyl, which may be substituted by Cl, CN, ##STR21## with n=1, 2 or 3, benzyl, or 2-phenethyl, R₇ ''' represents hydrogen C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy or halogen,

R₉ ' represents hydrogen, chlorine, methyl, ethyl, methoxy or ethoxy and

R₁₃ ' represents hydrogen, C₁ -C₄ -alkyl or phenyl which is optionally substituted by nitro, halogen, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy.

Particularly preferred dyestuffs are those which in the form of the free acid correspond to the formula ##STR22## and to the formula ##STR23## wherein p represents 0 or 1 and

B^(V) represents ##STR24## R₁ ', R₂ ', R₈ ', R₁₀ ', R₁₁ and R₁₂ ' have the abovementioned meaning.

Furthermore,

X' represents OH, --NH--SO₂ --R₃ ', ##STR25## or ##STR26## R₃ ' represents unsubstituted C₁ -C₄ -alkyl, o-, m- or p-toloyl or o-, m- or p-chlorophenyl,

R₄ ' represents hydrogen, methyl, or ethyl,

R₅ " and R₆ ^(IV) represent hydrogen, C₁ -C₄ -alkyl, which can be substituted by Cl, CN, ##STR27## or ##STR28## with n=1, 2 or 3, benzyl or 2-phenylethyl, R₇ ^(IV) presents hydrogen, methyl, ethyl, methoxy or ethoxy,

R₁₃ " represents hydrogen, C₁ -C₄ -alkyl which is not substituted further, or phenyl which can be monosubstituted or disubstituted by CH₃ or chlorine,

R₁₄ ' and R₁₅ ' represent C₁ -C₄ -alkyl which is not substituted further,

R₁₆ ' represents CN, ##STR29## with n=1, 2, 3 or 4 and R₁₇ " and R₁₉ ' represent hydrogen, methyl, ethyl, chlorine , bromine or trifluoromethyl.

Very particularly preferred dyestuffs are those which in the form of the free acid correspond to the formula ##STR30## and R₁ ", R₂ ", R₅ ", R₆ ^(IV), R₇ ^(IV), R₈ ', R₁₇ ", R₁₉ ' and X' have the abovementioned meaning.

Dyestuffs of the formula (I) are obtained by coupling a diazotised amine of the formula

    (X-SO.sub.2).sub.m -(CH.sub.2).sub.p -A-NH.sub.2

wherein

X, m, p and A have the abovementioned meaning,

to a thiophene of the formula ##STR31## wherein R₁ and R₂ have the abovementioned meaning,

and renewed diazotisation of the resulting dyestuff of the formula ##STR32## wherein X, m, p, A, R₁ and R₂ have the abovementioned meaning, following by coupling with a coupling component of the formula

    B-(SO.sub.3 H).sub.n

wherein

B and n have the abovementioned meaning.

Examples of amines suitable for use as diazo components are: 2-aminonaphthalene-1-sulphonic acid, 4-aminonaphthalene-1-sulphonic acid, 5-aminonaphthalene-1-sulphonic acid, 6-aminonaphthalene-1-sulphonic acid, 7-aminonaphthalene-1-sulphonic acid, 8-aminonaphthalene-1-sulphonic acid, 1-aminonaphthalene-2-sulphonic acid, 4-aminonaphthalene-2-sulphonic acid, 5-aminonaphthalene-2-sulphonic acid, 6-aminonaphthalene-2-sulphonic acid, 7-aminonaphthalene-2-sulphonic acid, 8-aminonaphthalene-2-sulphonic acid, 2-aminobenzenesulphonic acid, 4-chloro-2-aminobenzenesulphonic acid, aniline, 2-, 3- or 4-chloroaniline, 2,5-dichloroaniline, 2,4-dichloroaniline, 3-bromoaniline, 2-bromoaniline, 2-trifluoromethylaniline, 2-, 3- or 4-toluidine, 2-, 3- or 4-anisidine, 2-ethylaniline, 4-propoxyaniline, 4-benzylsulphonylaniline, 2-chloro-4-ethylsulphonylaniline, 2,5-dichloro-4-propylsulphonylaniline, aniline-4-N,N-dimethylsulphonamide, 2-chloroaniline-4-sulphonamide, 2-trifluoromethylaniline-4-N-benzylsulphonamide, 2,5-dichloroaniline-4-sulphonanilide, 2-chloroaniline-4-(2-methyl)-sulphonanilide, 2,5-dichloroaniline-4-N-hydroxypropylsulphonamide, 2-chloroaniline-4-N-cyclohexylsulphonamide-2-trifluoromethylaniline-4-N-methyl-N-phenylsulphonamide, 2-chloro-5-bromoaniline-4-N,N-dimethylsulphonamide, 2-chloro-6-methylaniline-4-N-methylsulphonamide, 2,5-dibromoaniline-4-N-benzylsulphonamide, aniline-4-sulphonic acid, 2-chloroaniline-4-sulphonic acid, 2,5-dichloroaniline-4-sulphonic acid, 2,5-dibromoaniline-4-sulphonic acid, 2-trifluoromethylaniline-5-sulphonic acid, 2-bromoaniline-4-sulphonic acid, 2,6-dibromoaniline-4-sulphonic acid, 2,6-dicyanoaniline-4-sulphonic acid, 2-trifluoromethyl-5-chloroaniline-4-sulphonic acid, 2-methylaniline-4-sulphonic acid, 3-methylaniline-4-sulphonic acid, 3-chloroaniline-5-sulphonic acid, 2,5-dimethoxyaniline-4-sulphonic acid, 1-aminonaphthalene-4-sulphonic acid, (3-amino-4-chlorobenzenesulphonyl)-methanesulphonamide, (3-amino-4-chlorobenzenesulphonyl)-butanesulphonamide, (3-amino-4-chlorobenzenesulphonyl)-o-toluenesulphonamide, (3-amino-4-chlorobenzenesulphonyl)-benzenesulphonamide, (3-amino-6-methylbenzenesulphonyl)-benzenesulphonamide, (3-amino-6-methoxybenzenesulphonyl)-butanesulphonamide, (4-aminobenzenesulphonyl)-p-toluenesulphonamide, (4-aminobenzenesulphonyl)-o-toluenesulphonamide, (4-aminobenzenesulphonyl)-methylsulphonamide, (4-aminobenzenesulphonyl)-butanesulphonamide, (4-amino-3-trifluoromethylbenzenesulphonyl)-benzenesulphonamide, (4-amino-3-trifluoromethylbenzenesulphonyl)-methanesulphonamide, (4-amino-3-trifluoromethylbenzenesulphonyl)-butanesulphonamide, (4-amino-3-trifluoromethylbenzenesulphonyl)-p-toluenesulphonamide, (4-amino-3-trifluoromethylbenzenesulphonyl)-o-toluenesulphonamide, (4-amino-3-trifluoromethylbenzenesulphonyl)-2-naphthylsulphonamide, (4-amino-3-chlorobenzenesulphonyl)-benzenesulphonamide, (4-amino-3-chlorobenzenesulphonyl)-p-toluenesulphonamide, (4-amino-3-chlorobenzenesulphonyl)-methanesulphonamide, (4-amino-3-chlorobenzenesulphonyl)-dimethylaminosulphonamide, (4-amino-3-bromobenzenesulphonyl)-benzenesulphonamide, (4-amino-3-methylbenzenesulphonyl)-benzenesulphonamide, (4-amino-3-methylbenzenesulphonyl)-p-toluenesulphonamide, (4-amino-2,5-dichlorobenzenesulphonyl)-benzenesulphonamide, (4-amino-2,5-dichlorobenzenesulphonyl)-propanesulphonamide, (4-amino-2,5-dichlorobenzenesulphonyl)-p-toluenesulphonamide, (4-amino-2,5-dichlorobenzenesulphonyl)-dimethylaminosulphonamide, (4-amino-3,5-dichlorobenzenesulphonyl)-benzenesulphonamide, (4-amino-2-chloro-5-trifluoromethylbenzenesulphonyl)-benzenesulphonamide, (4-amino-2-chloro-5-trifluoromethylbenzenesulphonyl)-methanesulphonamide, (4-amino-2-chloro-5-trifluoromethylbenzenesulphonyl)-2-naphthylsulphonamide, (4-amino-2-trifluoromethyl-5-chlorobenzenesulphonyl)-benzenesulphonamide,(4-amino-2-trifluoromethyl-5-chlorobenzenesulphonyl)-2-naphthylsulphonamide, (4-amino-2-trifluoromethyl-5-bromobenzenesulphonyl)-butanesulphonamide, (4-amino-2-trifluoromethylbenzenesulphonyl)-methanesulphonamide, (4-amino-2-trifluoromethylbenzenesulphonyl)-butanesulphonamide, (4-amino-2-methyl-5-chlorobenzenesulphonyl)-p-toluenesulphonamide, (4-amino-2-methyl-5-chlorobenzenesulphonyl)-o-toluenesulphonamide, (4-amino-2,5-dibromobenzenesulphonyl)-benzenesulphonamide, (4-amino-2,5-dimethylbenzenesulphonyl)-butanesulphonamide, N-(4-aminophenylsulphonyl)-2-aminoethanesulphonic acid, N-methyl-N-(4-aminophenylsulphonyl)-2-aminoethanesulphonic acid, N-propyl-N-(4-aminophenylsulphonyl)-2-aminoethanesulphonic acid, N-(4-amino-2-chlorophenylsulphonyl)-2-aminoethanesulphonic acid, N-ethyl-N-(4-amino-2-chlorophenylsulphonyl)-2-aminoethanesulphonic acid, N-(4-amino-3-chlorophenylsulphonyl)-2-aminoethanesulphonic acid, N-methyl-N-(4-amino-3-chlorophenylsulphonyl)-2-aminoethanesulphonic acid, N-ethyl-N-(4-amino-3-chlorophenylsulphonyl)-2-aminoethanesulphonic acid, N-(4-amino-2,5-dichlorophenylsulphonyl)-2-aminoethanesulphonic acid, N-methyl-N-(4-amino-2,5-dichlorophenylsulphonyl)-2-aminoethanesulphonic acid, N-ethyl-N-(4-amino-2,5-dichlorophenylsulphonyl)-2-aminoethanesulphonic acid, N-(4-amino-3,5-dichlorophenylsulphonyl)-2-aminoethanesulphonic acid, N-methyl-N-(4-amino-3,5-dichlorophenylsulphonyl)-2-aminoethanesulphonic acid, N-(4-aminophenylsulphonyl)-2-aminoethanesulphonic acid, N-methyl-N-(4-aminophenylsulphonyl)-2-aminoethanesulphonic acid, N-(4-amino-2-chlorophenylsulphonyl)-2-aminoethanesulphonic acid, N-ethyl-N-(4-amino-2-chlorophenylsulphonyl)-2-aminoethanesulphonic acid, N-(4-amino-3-chlorophenylsulphonyl)-2-aminoethanesulphonic acid, N-methyl-N-(4-amino-3-chlorophenylsulphonyl)-2-aminoethanesulphonic acid, N-ethyl-N-(4-amino-3-chlorophenylsulphonyl)-2-aminoethanesulphonic acid, N-(4-amino-2,5-dichlorophenylsulphonyl)-2-aminoethanesulphonic acid, N-methyl-N-(4-amino-2,5-dichlorophenylsulphonyl)-2-aminoethanesulphonic acid, N-ethyl-N-(4-amino-2,5-dichlorophenylsulphonyl)-2-aminoethanesulphonic acid, N-(4-amino-3,5-dichlorophenylsulphonyl)-2-aminoethanesulphonic acid, N-methyl-N-(4-amino-3,5-dichlorophenylsulphonyl)-2-aminoethanesulphonic acid, N-(4-amino-3-methylphenylsulphonyl)-2-aminoethanesulphonic acid, N-(4-amino-3-methoxyphenylsulphonyl)-2-aminoethanesulphonic acid, N-methyl-N-(4-amino-3-methoxyphenylsulphonyl)-2-aminoethanesulphonic acid, N-(4-amino-3-trifluoromethylphenylsulphonyl)-2-aminoethanesulphonic acid, N-methyl-N-(4-amino-3-trifluoromethylphenylsulphonyl)-2-aminoethanesulphonic acid, N-propyl-N-(4-amino-3-trifluoromethylphenylsulphonyl)-2-aminoethanesulphonic acid, N-(4-aminophenylsulphonyl)-3-aminopropylsulphonic acid, N-methyl-N-(4-aminophenylsulphonyl)-3-aminopropylsulphonic acid, N-(4-amino-2-chlorophenylsulphonyl)-3-aminopropylsulphonic acid, N-(4-amino-2,5-dichlorophenylsulphonyl)-3-aminopropylsulphonic acid, N-(4-amino-3,5-dichlorophenylsulphonyl)-3-aminopropylsulphonic acid, N-propyl-N-(4-amino-3,5-dichlorophenylsulphonyl)-3-aminopropylsulphonic acid, N-(4-amino-3-trifluoromethylphenylsulphonyl)-3-aminopropylsulphonic acid, N-methyl-N-(4-amino-2,5-dichlorophenylsulphonyl)-3-aminobutylsulphonic acid, N-(4-amino-2,5-dichlorophenylsulphonyl)-3-aminophenylsulphonic acid, N-(4-amino-3-trifluoromethylphenylsulphonyl)-3-amino-phenylsulphonic acid, N-( 4-amino-2,5-dichlorophenylsulphonyl)-4-aminophenylsulphonic acid, N-methyl-N-(4-amino-2,5-dichlorophenyl)-sulphonyl)-4-aminophenylsulphonic acid, N-(4-amino-2,5-dichlorophenyl)-sulphonyl-2-aminoethyl-sulphonate, N-methyl-N-(4-amino-2,5-dichlorophenylsulphonyl)-2-aminoethyl-sulphate, N-ethyl-N-(4-amino-2-dichlorophenylsulphonyl)-2-aminoethylsulphate, N-(4-aminophenylsulphonyl)-2-aminoethyl-sulphate and N-methyl-N-(4-aminophenylsulphonyl)-2-amino-1-methylethylsulphate.

Examples of suitable aminothiophenes are: 2-amino-3-carbethoxythiophene, 2-amino-3-carbomethoxy-4-methylthiophene, 2-amino-3-cyanothiophene, 2-amino-3-cyano-4-ethylthiophene, 2-amino-3-cyano-4-methylthiophene, 2-amino-3-carbethoxy-4-carbethoxythiophene, 2-amino-3-carbethoxy-4-phenylthiophene, 2-amino-3-carbethoxy-4-(4-nitrophenyl)-thiophene, 2-amino-3-carbamoylthiophene, 2-amino-3-carbamoyl-4-methylthiophene and 2-amino-3-carbamoyl-4-phenylthiophene.

Examples of suitable coupling components for the diazotised monoazo dyestuffs are: N,N-diethylaniline, N,N-dipropylaniline, N,N-dibutylaniline, 3-methyl-N,N-diethylaniline, 3-methyl-N-ethyl-N-(2-cyanoethyl)-aniline, 3-methyl-N-ethyl-N-(2-methylcarbonyloxyethyl)-aniline, 3-methyl-N-(2-methyloxycarbonyloxyethyl)-N-ethylaniline, 3-ethyl-N,N-diethylaniline, 3-methyl-N,N-di-(2-ethoxycarbonyloxyethyl)-aniline, 3-methyl-N,N-di-(2-butoxycarbonyloxyethyl)-aniline, 3-acetylamino-N,N-diethylaniline, 3-acetylamino-N-ethyl-N-(2-ethoxycarbonyloxyethyl)-aniline, 3-acetylamino-N-ethyl-N-(2-cyanoethyl)-aniline, 3-acetylamino-N-(2-cyanoethyl)-N-(2-carbethoxycarbonyloxyethyl)-aniline, 3-(propylcarbonylamino)-N,N-diethylaniline, 3-(methylsulphonylamino)-N,N-diethylaniline, 3-(butylsulphonylamino)-N,N-diethylaniline, 3-(phenylsulphonylamino-N,N-diethylaniline, 3-acetylamino-6-ethoxy-N,N-diethylaniline, 3-acetylamino-6-methoxy-N,N-diethylaniline, 3-acetylamino-6-methoxy-N-ethyl-N-(2-cyanoethyl)-aniline, 3-acetylamino-6-methoxy-N,N-di-(2-ethoxycarbonyloxyethyl)-aniline, 3-chloro-N,N-diethylaniline, 3-chloro-N,N-dimethylaniline, 3-chloro-N-ethyl-N-(2-cyanoethyl)-aniline, 2-carbamoyl-N,N-diethylaniline, 2-carbethoxy-N,N-diethylaniline, N-ethyl-N-(2-sulphoethyl)-aniline, 3-methyl-N-ethyl-N-(2-sulphoethyl)-aniline, 3-methyl-N-benzyl-N-(2-sulphoethyl)-aniline, 3-methyl-N-ethyl-N-(3-sulphobenzyl)-aniline, N-ethyl-N-(3-sulphoebenzyl)-aniline, 3-methyl-N-methyl-N-(3-sulphobenzyl)-aniline, 3-methoxy-N-ethyl-N-(3-sulphobenzyl)-aniline, 3-acetamino-N-butyl-N-(3-sulphobenzyl)-aniline, 8-anilinonaphthalene-1-sulphonic acid, 8-p-toluidinonaphthalene-1-sulphonic acid, N,N-diethyl-8-aminonaphthalene-1-sulphonic acid, N,N-diethyl-5-aminonaphthalene-2-sulphonic acid, N-ethyl-N-(2-cyanoethyl)-5-aminonaphthalene-2-sulphonic acid, indole, 1-methylindole, 3-methylindole, 2-phenylindole, 2-ethylindole, 1-methyl-2-phenylindole, 2-phenylindolesulphonic acid, 1-methylindolesulphonic acid, 1-(2-hydroxypropyl)-2-methylindole, 1-(2-hydroxybutyl)-2-methylindole, 1-(2-hydroxy-2-phenylethyl)-2-methylindole, 1-(2-hydroxy-2-methylpropyl)-2-methylindole, 1-(2-hydroxy-3-phenoxypropyl)-2-methylindole, 1-(1-hydroxypropyl-2)-2-methylindole, 1-(2-hydroxypropyl)-2-phenylindole, 1-(2-hydroxybutyl)-2-phenylindole, 1-(2-hydroxy-2-phenylethyl)-2-phenylindole, 1-(2-hydroxy-2-methylpropyl)-phenylindole, 1-(2-hydroxy-3-phenoxypropyl)-2 -phenylindole, 1-(1-hydroxypropyl-2)-2-phenylindole, 1-(2-hydroxypropyl)-2-methylindolesulphonic acid, 1-(2-hydroxybutyl-2-methylindolesulphonic acid, 1-(2-hydroxy-2-phenylethyl)-2-methylindolesulphonic acid, 1-(2-hydroxy-2-methylpropyl)-2-methylindolesulphonic acid, 1-(2-hydroxy-3-phenoxypropyl)-2-methylindolesulphonic acid, 1-(1-hydroxypropyl-2)-2-methylindolesulphonic acid, 1-(2-hydroxypropyl)-2-phenylindolesulphonic acid, 1-(2-hydroxybutyl)-2-phenylindolesulphonic acid, 1-(2-hydroxy-2-phenylethyl)-2-phenylindolesulphonic acid, 1-(2-hydroxy-2-methylpropyl)-2-phenylindolesulphonic acid, 1-(2-hydroxy-3-phenoxypropyl)-2-phenylindolesulphonic acid, 1-(1-hydroxypropyl-2)-2-phenyl-indolesulphonic acid, 3-methyl-5-pyrazolone, 1-phenyl-3-methyl-5-pyrazolone, 1-(2-chlorophenyl)-3-methyl-5-pyrazolone, 1-(2,5-dichlorophenyl)-3-methyl-5-pyrazolone, 1-p-tolyl-3-ethyl-5-pyrazolone, 1-(3-sulphamoylphenyl)-3-methyl-5-pyrazolone, 1-(2-sulphophenyl)-3-methyl-5-pyrazolone, 1-(3-sulphophenyl)-3-methyl-5-pyrazolone, 1-(6-chloro-3-sulphophenyl)-3-methyl-5-pyrazolone, 1-(3-sulphophenyl)-5-amino-3-methylpyrazolone, 1-(4-sulphophenyl)-3-methyl-5-pyrazolone, 1-(2-chloro-4-sulphophenyl)-3-methyl-5-pyrazolone, 1-(2,5-dichloro-4-sulphophenyl)-3-methyl-5-pyrazolone, 1-(6-chloro-4-sulphone-2-methylphenyl)-3-methyl-5-pyrazolone, 1-(6-chloro-4-sulpho-2-ethylphenyl)-5-amino-3-methylpyrazole, 1-(2-sulphophenyl)-5-amino-3-methylpyrazole, 1-(3-sulphophenyl)-5-amino-3-ethylpyrazole, 1-(4-sulphophenyl)-5-amino-3-methylpyrazole, 1-phenyl-3-methyl-5-aminopyrazole, 1-(2-sulphophenyl)-3-phenyl-5-pyrazolone, 1-phenyl-3-phenyl-5-pyrazolone, 1-(3-sulphophenyl)-3-(4-nitrophenyl)-5-pyrazolone, 1-phenyl-5-pyrazolone-3-carboxylic acid ethyl ester, 1-phenyl-5-pyrazolone-3-carboxylic acid amide, 1-(6-chloro-4-sulpho-2-methylphenyl)-5-pyrazolone-3-carboxylic acid ethyl ester, 1,4-dimethyl-5-cyano-2,6-pyridione, 1-propyl-4-methyl-5-cyano-2,6-pyridione, 1-butyl-4-ethyl-5-carbamoyl-2,6-pyridione, 1-ethyl-4-methyl-5-carbethoxy-2,6-pyridione, 1-methyl-4,5-dicarbomethoxy-2,6-pyridione and 1-propyl-4,6-dihydroxypyridione-2-pyridione.

The dyestuffs according to the invention are suitable for dyeing natural and synthetic fibre materials, particularly for dyeing polyamide in level violet to blue-green shades of good yield and good fastness properties in use. They are absorbed well on polyamide even in a neutral to weakly acid dyebath. By polyamide fibres there are here especially to be understood fibres of synthetic polyamides such as ε-polycaprolactam or condensation products of adipic acid and hexamethylenediamine.

EXAMPLE 1

4.7 g of 2,6-dichloroaniline are stirred into 200 ml of glacial acetic acid and 20 ml of concentrated hydrochloric acid, the mixture is cooled to 0° C. and a solution of 2 g of NaNO₂ in 20 ml of H₂ O is added dropwise. After about 2 hours, the diazonium salt solution is added slowly to a solution of 5.08 g of 2-amino-3-carbethoxythophene and the mixture is buffered to pH 2 with a saturated sodium acetate solution. The resulting dyestuff, of the formula ##STR33## is filtered off and dried at 40° C.

2.2 g of the dyestuff of the formula (1) are dissolved in 25 ml of 80% strength phosphoric acid and 25 ml of glacial acetic acid. The solution is cooled to 0° C. and 2.6 ml of 45% strength nitrosysulphuric acid are added dropwise. The mixture is stirred for 3 hours at 0° C., the excess nitrosylsulphuric acid is destroyed with urea and 2.3 g of N-ethyl-N-(3-sulphobenzyl)-3-methylaniline dissolved in 40 ml of glacial acetic acid are added. The reaction mixture is then introduced into 350 ml of saturated sodium acetate solution and 100 g of ice. The resulting dyestuff of the formula ##STR34## is filtered off and dried at 40° C.

Dyeing example:

0.1 g of the dyestuff from Example 1 is dissolved in 100 ml of hot water, 5 ml of 10% strength ammonium acetate solution are added and the mixture is diluted to a volume of 500 ml with water. 10 g of polyamide fibre are introduced into the dyebath, the latter is brought to the boil over the course of 20 minutes, 4 ml of 10% strength acetic acid are added and the bath is kept at the boil for one hour. The fibres are then rinsed and dried at 70°-80° C. A dyeing in a navy-blue shade, having good fastness properties in use, is obtained.

EXAMPLE 2

2.94 g of p-sulphanilic acid are dissolved in 30 ml of water and 0.8 g of NaOH and 1 g of NaNO₂ are added. 100 g of ice and 10 ml of concentrated hydrochloric acid are then introduced. The mixture is stirred for two hours at 0° C. Thereafter, 2.54 g of 2-amino-3-carbethoxythiophene, dissolved in 100 ml of methanol, are added. The dyestuff which has precipitated, of the formula ##STR35## is filtered off and dried at 40° C.

2.5 g of this dyestuff are stirred with 25 ml of phosphoric acid and 25 ml of glacial acetic acid, cooled to 0° C. and diazotised for 3 to 4 hours with 2.6 g of 40% strength nitrosylsulphuric acid. 1 g of urea is then added and 1.4 g of N-ethyl-N-2'-cyanoethyltoluidine dissolved in 30 ml of glacial acetic acid are added. The reaction mixture is introduced into 100 g of ice and 350 ml of concentrated sodium acetate solution. The dyestuff which has precipitated, of the formula ##STR36## reddish-tinged blue is filtered off and dried at 40° C.

If the procedure in Example 1 and 2 is followed, the amines indicated in column 1 are used as the diazo component, the thiophenes indicated in column 2 are used as the middle component and the compounds indicated in column 3 are used as the coupling component, water-soluble dyestuffs are obtained, which dye polyamide from a weakly acid or neutral bath in violet to blue-green light-fast shades.

                                      Table I                                      __________________________________________________________________________     I                              II              III                             __________________________________________________________________________         ##STR37##                                                                                                  ##STR38##                                                                                      ##STR39##                      4                                                                                  ##STR40##                  "               "                               5                                                                                  ##STR41##                  "               "                               6                                                                                  ##STR42##                  "               "                               7                                                                                  ##STR43##                  "               "                               8                                                                                  ##STR44##                  "               "                               9                                                                                  ##STR45##                  "               "                               10                                                                                 ##STR46##                  "               "                               11                                                                                 ##STR47##                  "               "                               12                                                                                 ##STR48##                  "               "                               13                                                                                 ##STR49##                  "               "                               14                                                                                 ##STR50##                  "               "                               15                                                                                 ##STR51##                  "               "                               16                                                                                 ##STR52##                                                                                                  ##STR53##      "                               17                                                                                 ##STR54##                  "               "                               18                                                                                 ##STR55##                  "               "                               19                                                                                 ##STR56##                  "               "                               20                                                                                 ##STR57##                                                                                                  ##STR58##      "                               21                                                                                 ##STR59##                  "                                                                                               ##STR60##                      22                                                                                 ##STR61##                  "               "                               23                                                                                 ##STR62##                  "               "                               24                                                                                 ##STR63##                  "                                                                                               ##STR64##                      25                                                                                 ##STR65##                                                                                                  ##STR66##      "                               26                                                                                 ##STR67##                                                                                                  ##STR68##      "                               27                                                                                 ##STR69##                  "               "                               28                                                                                 ##STR70##                  "               "                               29                                                                                 ##STR71##                  "               "                               30                                                                                 ##STR72##                  "               "                               31                                                                                 ##STR73##                  "               "                               32                                                                                 ##STR74##                  "               "                               33                                                                                 ##STR75##                  "               "                               34                                                                                 ##STR76##                  "                                                                                               ##STR77##                      35                                                                                 ##STR78##                  "               "                               36                                                                                 ##STR79##                  "                                                                                               ##STR80##                      37                                                                                 ##STR81##                  "               "                               38                                                                                 ##STR82##                  "               "                               39                                                                                 ##STR83##                  "               "                               40                                                                                 ##STR84##                  "               "                               41                                                                                 ##STR85##                  "                                                                                               ##STR86##                      42                                                                                 ##STR87##                                                                                                  ##STR88##                                                                                      ##STR89##                      43                                                                                 ##STR90##                  "               "                               44                                                                                 ##STR91##                  "               "                               45                                                                                 ##STR92##                                                                                                  ##STR93##                                                                                      ##STR94##                      46                                                                                 ##STR95##                  "               "                               47                                                                                 ##STR96##                  "                                                                                               ##STR97##                      48                                                                                 ##STR98##                  "                                                                                               ##STR99##                      49                                                                                 ##STR100##                                                                                                 ##STR101##                                                                                     ##STR102##                     50                                                                                 ##STR103##                 "                                                                                               ##STR104##                     51                                                                                 ##STR105##                 "                                                                                               ##STR106##                     52                                                                                 ##STR107##                 "                                                                                               ##STR108##                     53                                                                                 ##STR109##                 "                                                                                               ##STR110##                     54                                                                                 ##STR111##                 "                                                                                               ##STR112##                     55                                                                                 ##STR113##                 "                                                                                               ##STR114##                     56                                                                                 ##STR115##                                                                                                 ##STR116##                                                                                     ##STR117##                     57                                                                                 ##STR118##                 "                                                                                               ##STR119##                     58 "                           "                                                                                               ##STR120##                     59                                                                                 ##STR121##                 "                                                                                               ##STR122##                     60                                                                                 ##STR123##                                                                                                 ##STR124##                                                                                     ##STR125##                     61                                                                                 ##STR126##                 "                                                                                               ##STR127##                     62                                                                                 ##STR128##                 "                                                                                               ##STR129##                     63                                                                                 ##STR130##                                                                                                 ##STR131##                                                                                     ##STR132##                     64                                                                                 ##STR133##                 "                                                                                               ##STR134##                     65                                                                                 ##STR135##                 "                                                                                               ##STR136##                     66                                                                                 ##STR137##                 "                                                                                               ##STR138##                     67                                                                                 ##STR139##                                                                                                 ##STR140##                                                                                     ##STR141##                     68                                                                                 ##STR142##                 "                                                                                               ##STR143##                     69                                                                                 ##STR144##                                                                                                 ##STR145##                                                                                     ##STR146##                     70                                                                                 ##STR147##                 "                                                                                               ##STR148##                     71                                                                                 ##STR149##                 "                                                                                               ##STR150##                     72                                                                                 ##STR151##                 "                                                                                               ##STR152##                     73                                                                                 ##STR153##                 "                                                                                               ##STR154##                     74                                                                                 ##STR155##                 "                                                                                               ##STR156##                     75                                                                                 ##STR157##                 "                                                                                               ##STR158##                     76                                                                                 ##STR159##                                                                                                 ##STR160##                                                                                     ##STR161##                     77                                                                                 ##STR162##                 "               "                               78                                                                                 ##STR163##                 "                                                                                               ##STR164##                     79                                                                                 ##STR165##                 "                                                                                               ##STR166##                     80                                                                                 ##STR167##                 "                                                                                               ##STR168##                     81                                                                                 ##STR169##                 "                                                                                               ##STR170##                     82                                                                                 ##STR171##                 "                                                                                               ##STR172##                     83                                                                                 ##STR173##                 "                                                                                               ##STR174##                     84                                                                                 ##STR175##                                                                                                 ##STR176##                                                                                     ##STR177##                     85                                                                                 ##STR178##                 "                                                                                               ##STR179##                     86                                                                                 ##STR180##                 "                                                                                               ##STR181##                     87                                                                                 ##STR182##                 "                                                                                               ##STR183##                     88                                                                                 ##STR184##                 "                                                                                               ##STR185##                     89                                                                                 ##STR186##                 "                                                                                               ##STR187##                     90                                                                                 ##STR188##                                                                                                 ##STR189##                                                                                     ##STR190##                     91                                                                                 ##STR191##                 "                                                                                               ##STR192##                     92                                                                                 ##STR193##                                                                                                 ##STR194##                                                                                     ##STR195##                     93                                                                                 ##STR196##                 "                                                                                               ##STR197##                     94                                                                                 ##STR198##                 "                                                                                               ##STR199##                     95                                                                                 ##STR200##                 "                                                                                               ##STR201##                     96                                                                                 ##STR202##                 "                                                                                               ##STR203##                     97                                                                                 ##STR204##                                                                                                 ##STR205##                                                                                     ##STR206##                     98                                                                                 ##STR207##                 "                                                                                               ##STR208##                     99                                                                                 ##STR209##                 "                                                                                               ##STR210##                     100                                                                                ##STR211##                 "                                                                                               ##STR212##                     101                                                                                ##STR213##                                                                                                 ##STR214##                                                                                     ##STR215##                     102                                                                                ##STR216##                 "                                                                                               ##STR217##                     103                                                                                ##STR218##                 "                                                                                               ##STR219##                     104                                                                                ##STR220##                 "                                                                                               ##STR221##                     105                                                                                ##STR222##                 "                                                                                               ##STR223##                     106                                                                                ##STR224##                 "                                                                                               ##STR225##                     107                                                                                ##STR226##                                                                                                 ##STR227##                                                                                     ##STR228##                     108                                                                                ##STR229##                 "                                                                                               ##STR230##                     109                                                                                ##STR231##                                                                                                 ##STR232##                                                                                     ##STR233##                     100                                                                                ##STR234##                 "                                                                                               ##STR235##                     111                                                                                ##STR236##                                                                                                 ##STR237##                                                                                     ##STR238##                     112                                                                                ##STR239##                 "                                                                                               ##STR240##                     113                                                                                ##STR241##                 "                                                                                               ##STR242##                     114                                                                                ##STR243##                 "                                                                                               ##STR244##                     115                                                                                ##STR245##                 "                                                                                               ##STR246##                     116                                                                                ##STR247##                                                                                                 ##STR248##                                                                                     ##STR249##                     117                                                                                ##STR250##                 "                                                                                               ##STR251##                     118                                                                                ##STR252##                 "                                                                                               ##STR253##                     119                                                                                ##STR254##                 "                                                                                               ##STR255##                     120                                                                                ##STR256##                 "                                                                                               ##STR257##                     121                                                                                ##STR258##                 "                                                                                               ##STR259##                     122                                                                                ##STR260##                                                                                                 ##STR261##                                                                                     ##STR262##                     123                                                                                ##STR263##                 "                                                                                               ##STR264##                     124                                                                                ##STR265##                 "                                                                                               ##STR266##                     125                                                                                ##STR267##                 "                                                                                               ##STR268##                     126                                                                                ##STR269##                                                                                                 ##STR270##                                                                                     ##STR271##                     127                                                                                ##STR272##                 "                                                                                               ##STR273##                     128                                                                                ##STR274##                 "                                                                                               ##STR275##                     129                                                                                ##STR276##                 "                                                                                               ##STR277##                     130                                                                                ##STR278##                 "                                                                                               ##STR279##                     131                                                                                ##STR280##                 "                                                                                               ##STR281##                     132                                                                                ##STR282##                 "                                                                                               ##STR283##                     133                                                                                ##STR284##                 "                                                                                               ##STR285##                     134                                                                                ##STR286##                 "                                                                                               ##STR287##                     135                                                                                ##STR288##                 "                                                                                               ##STR289##                     136                                                                                ##STR290##                                                                                                 ##STR291##                                                                                     ##STR292##                     137                                                                                ##STR293##                 "                                                                                               ##STR294##                     138                                                                                ##STR295##                 "                                                                                               ##STR296##                     139                                                                                ##STR297##                 "                                                                                               ##STR298##                     140                                                                                ##STR299##                 "               "                               141                                                                                ##STR300##                 "               "                               142                                                                                ##STR301##                 "               "                               143                                                                                ##STR302##                                                                                                 ##STR303##     "                               144                                                                                ##STR304##                                                                                                 ##STR305##     "                               145                                                                               "                           "                                                                                               ##STR306##                     146                                                                                ##STR307##                 "                                                                                               ##STR308##                     147                                                                                ##STR309##                 "                                                                                               ##STR310##                     148                                                                                ##STR311##                                                                                                 ##STR312##                                                                                     ##STR313##                     149                                                                                ##STR314##                                                                                                 ##STR315##                                                                                     ##STR316##                     150                                                                                ##STR317##                 "                                                                                               ##STR318##                     151                                                                                ##STR319##                                                                                                 ##STR320##                                                                                     ##STR321##                     152                                                                                ##STR322##                 "                                                                                               ##STR323##                     153                                                                                ##STR324##                                                                                                 ##STR325##                                                                                     ##STR326##                     154                                                                                ##STR327##                                                                                                 ##STR328##                                                                                     ##STR329##                     155                                                                                ##STR330##                                                                                                 ##STR331##                                                                                     ##STR332##                     156                                                                                ##STR333##                                                                                                 ##STR334##                                                                                     ##STR335##                     157                                                                                ##STR336##                                                                                                 ##STR337##                                                                                     ##STR338##                     158                                                                                ##STR339##                                                                                                 ##STR340##                                                                                     ##STR341##                     159                                                                                ##STR342##                                                                                                 ##STR343##     "                               160                                                                                ##STR344##                                                                                                 ##STR345##                                                                                     ##STR346##                     161                                                                                ##STR347##                 "                                                                                               ##STR348##                     162                                                                                ##STR349##                 "               "                               163                                                                                ##STR350##                 "                                                                                               ##STR351##                     164                                                                                ##STR352##                                                                                                 ##STR353##                                                                                     ##STR354##                     165                                                                                ##STR355##                 "               "                               166                                                                                ##STR356##                                                                                                 ##STR357##                                                                                     ##STR358##                     167                                                                                ##STR359##                 "                                                                                               ##STR360##                     168                                                                                ##STR361##                 "                                                                                               ##STR362##                     169                                                                                ##STR363##                 "                                                                                               ##STR364##                     170                                                                                ##STR365##                                                                                                 ##STR366##                                                                                     ##STR367##                     171                                                                               "                                                                                                           ##STR368##     "                               172                                                                                ##STR369##                 "               "                               173                                                                                ##STR370##                 "                                                                                               ##STR371##                     174                                                                               "                                                                                                           ##STR372##     "                               175                                                                               "                                                                                                           ##STR373##                                                                                     ##STR374##                     __________________________________________________________________________ 

We claim:
 1. Acid disazo dyestuff of the formula ##STR375## wherein R₁ ' represents hydrogen, methyl, ethyl, carbo-C₁ -C₄ -alkoxy, phenyl, or phenyl substituted by Cl or NO₂ ;R₂ ' represents carbo-C₁ -C₄ -alkoxy, cyano, CONH₂, CON (CH₃)₂ or CON (C₂ H₅)₂ ; R₁₇ ' and R₁₈ ' represent hydrogen; chlorine; bromine; cyano; C₁ -C₂ -alkyl; C₁ -C₂ -alkoxy; C₂ -C₄ -carboalkoxy; carbamoyl; carbamoyl mono- or di-substituted by C₁ -C₃ -alkyl; sulphamoyl; sulphamoyl mono- or disubstituted by C₁ -C₃ -alkyl; C₁ -C₄ -alkylsulphonyl; phenylsulphonyl; or benzylsulphonyl; R₁₉ represents hydrogen, C₁ -C₄ -alkyl, CF₃, Cl, or Br; B" is a radical of a coupling component selected from the group consisting of: ##STR376## wherein R₅ ' represents hydrogen, C₁ -C₄ -alkyl, or benzyl; R₆ ' represents C₁ -C₄ -alkyl, CH₂ --CH₂ --SO₃ H, or 3-sulphobenzyl; R₆ " represents hydrogen, C₁ -C₄ -alkyl, benzyl, or 2-phenylethyl; R₇ ' represents hydrogen, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, halogen, or C₁ -C₄ -alkylsulphonyl; R₈ ' represents hydrogen, CH₃, C₂ H₅, OCH₃, OC₂ H₅, Cl, or NH--CO--(CH₂)_(n) --H with n=1, 2 or 3, R₁₀ ' represents methyl, ethyl or phenyl; R₁₁ represents hydrogen; C₁ -C₄ -alkyl; or C₁ -C₄ -alkyl substituted by halogen, cyano, hydroxyl, or C₁ -C₄ -alkoxy; R₁₂ ' represents hydrogen, methyl, phenyl, carbomethoxy or carboethoxy; and R₂₀ and R₂₁ represent hydrogen, C₁ -C₄ -alkyl, Cl, or Br.
 2. Acid dyestuff of claim 1 of the formula ##STR377## wherein R₁ " denotes hydrogen, methyl or phenyl;R₂ " denotes carbomethoxy, carboethoxy, cyano or CONH₂ B"' is the radical of a coupling component selected from the group consisting of: ##STR378## wherein R₅ ', R₆ ', R₆ ", R₈ ', R₁₀ ', R₁₂ ' have the definition given in claim 1; R₇ " represents hydrogen, methoxy, ethoxy, or methylsulphonyl; R₁₁ ' represents hydrogen or methyl; and R₂₀ ' and R₂₁ ' represent hydrogen, methyl or chlorine.
 3. Acid dyestuff of claim 1 of the formula ##STR379## wherein R₁₇ ', R₁₈ ' and R₁₉ have the definition indicated in claim 1;R₁ " denotes hydrogen, methyl or phenyl; R₂ " denotes carbomethoxy, carboethoxy, cyano or CONH₂ ; R₈ " denotes hydrogen, methyl, methoxy, or acetylamino; and V represents ##STR380##
 4. Acid dyestuff of the formula ##STR381## wherein A represents ##STR382## B^(V) is a radical of a coupling component selected from the group consisting of: ##STR383## wherein R₁ ' represents hydrogen, methyl, ethyl, carbo-C₁ -C₄ -alkoxy, phenyl, or phenyl substituted by Cl or NO₂ ;R₂ ' represents carbo-C₁ -C₄ -alkoxy, CN, CONH₂, CON(CH₃)₂, or CON(C₂ H₅)₂ ; R" and R₆ IV represent hydrogen; benzyl; 2-phenylethyl; C₁ -C₄ -alkyl; or C₁ -C₄ -alkyl substituted by Cl, CN, O--CO--(CH₂)_(n) --H, or OCO--O(CH₂)_(n) H with n=1, 2 or 3; R₇ IV represents hydrogen, methyl, ethyl, methoxy, or ethoxy; R₈ ' represents H, CH₃, C₂ H₅, OCH₃, OC₂ H₅, Cl or --NH--CO--(CH₂)_(n) --H with n=1, 2 or 3; R₁₀ ' represents CH₃, C₂ H₅, or phenyl; R₁₁ represents hydrogen; C₁ -C₄ -alkyl; or C₁ -C₄ -alkyl substituted by halogen, cyano, hydroxyl or C₁ -C₄ -alkoxy; R₁₂ ' represents hydrogen, methyl, phenyl, carbomethoxy, or carboethoxy, R₁₃ " represents hydrogen, C₁ -C₄ -alkyl, phenyl, or phenyl mono- or disubstituted by CH₃ or Cl; R₁₄ ' and R₁₅ ' represent C₁ -C₄ -alkyl; R₁₆ ' represents CN, CONH₂, or CO--O--(CH₂)_(m) H with m=1, 2, 3 or 4; R₁₇ " and R₁₉ ' represent hydrogen, methyl, ethyl, chlorine, bromine, or CF₃ ; p represents 0 or 1; X' represents OH, NH--SO₂ R₃ ', ##STR384## or ##STR385## R₃ ' represents C₁ -C₄ -alkyl, tolyl, or chlorophenyl; and R₄ ' represents hydrogen, methyl, or ethyl.
 5. Acid dyestuffs of claim 4 of the formula ##STR386## wherein R₁ " represents H, CH₃, or phenyl;R₂ " represents COOCH₃, COOC₂ H₅, CN, or CONH₂ ; and X', R₅ ", R₆ ^(IV), R₇ ^(IV), R₈ ', R₁₇ " and R₁₉ ' have the meaning indicated in claim
 4. 